US9957244B2 - Catalyst and process for producing 2,5-furandicarboxylic acid from hydroxymethylfurfural in water - Google Patents

Catalyst and process for producing 2,5-furandicarboxylic acid from hydroxymethylfurfural in water Download PDF

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US9957244B2
US9957244B2 US15/500,367 US201515500367A US9957244B2 US 9957244 B2 US9957244 B2 US 9957244B2 US 201515500367 A US201515500367 A US 201515500367A US 9957244 B2 US9957244 B2 US 9957244B2
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hydroxymethylfurfural
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Alexandra Sanborn
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Archer Daniels Midland Co
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
    • C07D307/02—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings
    • C07D307/34—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
    • C07D307/56—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D307/68—Carbon atoms having three bonds to hetero atoms with at the most one bond to halogen
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
    • B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
    • B01J23/46—Ruthenium, rhodium, osmium or iridium
    • B01J23/462—Ruthenium
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
    • C07D307/02—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings
    • C07D307/34—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
    • C07D307/38—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with substituted hydrocarbon radicals attached to ring carbon atoms
    • C07D307/40—Radicals substituted by oxygen atoms
    • C07D307/42—Singly bound oxygen atoms
    • C07D307/44—Furfuryl alcohol
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/584—Recycling of catalysts

Definitions

  • the present invention relates to catalysts and related processes for producing 2,5-furandicarboxylic acid.
  • Agricultural raw materials such as starch, cellulose, sucrose or inulin are inexpensive and renewable starting materials for the manufacture of hexoses, such as glucose and fructose. It has long been appreciated in turn that glucose and other hexoses, in particular fructose, may be converted into other useful materials, such as 2-hydroxymethyl-5-furfuraldehyde, also known as 5-hydroxymethylfurfural or simply hydroxymethylfurfural (HMF):
  • HMF 2-hydroxymethyl-5-furfuraldehyde
  • HMF thus obtainable from hexoses such as fructose and glucose
  • hexoses such as fructose and glucose
  • renewable resources such as polymers, solvents, surfactants, pharmaceuticals, and plant protection agents.
  • HMF has in this regard been proposed, as either a starting material or intermediate, in the synthesis of a wide variety of compounds, such as furfuryl dialcohols, dialdehydes, esters, ethers, halides and carboxylic acids.
  • HMF hydroxymethylfurancarboxylic acid
  • FFCA formylfurancarboxylic acid
  • FDCA 2,5-furandicarboxylic acid
  • DFF diformylfuran
  • FDCA has been discussed as a biobased, renewable substitute in the production of such multi-megaton polyester polymers as poly(ethylene terephthalate) or poly(butylene terephthalate).
  • Derivatives such as FDCA can be made from 2,5-dihydroxymethylfuran and 2,5-bis(hydroxymethyl)tetrahydrofuran and used to make polyester polymers.
  • FDCA esters have also recently been evaluated as replacements for phthalate plasticizers for PVC, see, e.g., WO 2011/023491A1 and WO 2011/023590A1, both assigned to Evonik Oxeno GmbH, as well as R. D. Sanderson et al., Journal of Appl. Pol. Sci. 1994, vol. 53, pp. 1785-1793.
  • HMF and its oxidation-based derivatives such as FDCA have thus long been considered as promising biobased starting materials, intermediates and final products for a variety of applications, viable commercial-scale processes have proven elusive.
  • Acid-based dehydration methods have long been known for making HMF, being used at least as of 1895 to prepare HMF from levulose (Dull, Chem. Ztg., 19, 216) and from sucrose (Kiermayer, Chem. Ztg., 19, 1003).
  • these initial syntheses were not practical methods for producing HMF due to low conversion of the starting material to product.
  • Inexpensive inorganic acids such as H 2 SO 4 , H 3 PO 4 , and HCl have been used, but these are used in solution and are difficult to recycle.
  • solid sulfonic acid catalysts have also been used.
  • the solid acid resins have not proven entirely successful as alternatives, however, because of the formation of deactivating humin polymers on the surface of the resins.
  • Still other acid-catalyzed methods for forming HMF from hexose carbohydrates are described in Zhao et al., Science, Jun. 15, 2007, No. 316, pp. 1597-1600 and in Bicker et al., Green Chemistry, 2003, no. 5, pp. 280-284.
  • hexoses are treated with a metal salt such as chromium (II) chloride in the presence of an ionic liquid, at 100 degrees Celsius for three hours to result in a 70% yield of HMF, whereas in Bicker et al., sugars are dehydrocyclized to HMF at nearly 70% reported selectivity by the action of sub- or super-critical acetone and a sulfuric acid catalyst.
  • a metal salt such as chromium (II) chloride
  • HMF hydrogen fluoride
  • Another unwanted side reaction includes the polymerization of HMF and/or fructose resulting in humin polymers, which are solid waste products and act as catalyst poisons where solid acid resin catalysts are employed, as just mentioned.
  • HMF esters performs the conversion in the presence of an organic acid, which can also serve as the solvent.
  • Acetic acid is mentioned in particular as a solvent for fructose.
  • the resulting acetylated HMF product is reported to be “more stable” than HMF, because upon heating HMF is described as decomposing and producing byproducts “that are not easily isolated or removed,” page 4, paragraph 0048. Sanborn et al.
  • an aqueous hexose solution is rapidly heated from an ambient to a reaction temperature in the presence of an acid catalyst, with a limited per-pass conversion of the hexose sugars to HMF prior to separation of a fermentation-ready residual sugars product from the HMF product.
  • an acid catalyst By carrying out a rapid dehydration of the hexose sugars in this fashion, the overall exposure of the HMF that is formed to acidic, elevated temperature conditions is correspondingly limited.
  • the residual sugars product can be recycled for conversion to additional HMF, can be fermented to produce various products or put to other uses as referenced in the WO'136 application.
  • U.S. Pat. No. 8,193,382 to Lilga et al. describes oxidizing HMF in an aqueous solution with air or oxygen using a heterogeneous supported platinum catalyst.
  • the aqueous HMF starting material can be basic, neutral or acidic, though the “relatively low solubility” of HMF oxidation products such as FDCA in neutral and acidic water requires that “appropriate reactor designs” are utilized to accommodate solids formation or that the HMF concentration in the feed is limited to avoid generating FDCA concentrations over the solubility limit in a combination of acetic acid and water; in the alternative, it is said that “solids formation and feed concentration are typically not problematic” under “mildly basic conditions” generating a carboxylate salt of FDCA (col.
  • the oxidation catalysts are prepared by a complex method which involves calcination, mixing with platinum (II) acetylacetonate, rotary evaporation, repeated calcination, and reduction under hydrogen to an activated product, and then passivation under a flow of 2% O2.
  • JP Patent Application Publication 2009-23916 differs somewhat in employing cupric bromide, 2,2′-bipyridine and (2,2,6,6,-tetramethylpiperidin-1-yl)oxyl (TEMPO) in an alkaline aqueous HMF solution to produce FDCA carboxylate salts by use of both the Cannizzaro reaction and oxidation. From 5.0 to 20 equivalents of alkali are indicated as most preferred for each molar equivalent of HMF, so that while the use of a precious metal catalyst is avoided, the process still does have the same “serious limitation” ascribed by Zope et al. to the processes using such precious metal catalysts.
  • TEMPO 2,2,6,6,-tetramethylpiperidin-1-yloxyl
  • the present invention in one aspect, thus concerns a process for converting HMF to furanic products inclusive of FDCA, wherein a quantity of HMF is combined with water to provide an aqueous solution containing HMF in a concentration of at least about five percent by weight, and the aqueous solution containing HMF is combined with an oxygen source in the presence of a heterogeneous ruthenium-based catalyst and under conditions which are effective for oxidizing HMF to form furanic oxidation products inclusive of FDCA in the presence of the catalyst, but in the substantial absence of any solvent other than water.
  • the catalyst has ruthenium as its sole active catalytic component.
  • the catalyst is unsupported.
  • the catalyst is an unsupported ruthenium oxide catalyst.
  • the FDCA formed is hot-filtered away from the heterogeneous oxidation catalyst at a temperature sufficient to maintain the FDCA substantially entirely in an aqueous solution, and then precipitated from solution by cooling to recover a solid FDCA product.
  • FDCA is separated from the catalyst by dissolution in a solvent which does not substantially solubilize the catalyst, for example, methanol, followed by filtration to recover the catalyst and by removal of the solvent to provide a high purity FDCA solid product.
  • a solvent which does not substantially solubilize the catalyst for example, methanol
  • the FDCA is derivatized in situ to provide a more water-soluble FDCA derivative (for example, a dimethyl ester of FDCA) that can then be filtered away from the solid catalyst for further use or further processed to recover the underivatized FDCA.
  • a more water-soluble FDCA derivative for example, a dimethyl ester of FDCA
  • the present invention relates to an integrated process for making FDCA from an aqueous hexose solution, wherein a process according to the incorporated earlier WO'136 application is used to produce an aqueous feed comprising one or more hexose dehydration products inclusive at least of HMF, and HMF in the aqueous feed is oxidized to produce FDCA using a catalyst and process according to the instant application.
  • a fast-dehydration process as described in the WO'136 application is first used to generate an aqueous HMF product and a residual sugars product, with the aqueous HMF product then being used to provide the aqueous feed for an oxidation process according to the present invention (in certain embodiments, this will require addition of dilution water to generate an aqueous feed for the oxidation having a desired concentration of HMF in water) and the residual sugars product being recycled to provide additional HMF, used to make other products by fermentation, or used in still other ways as previously described in the WO '136 application.
  • the upstream fast-dehydration process for generating an aqueous HMF product can be operated in such a manner as to convert more or less of the hexose sugars to HMF as compared to the various other products that could be made from the hexose sugars, by means of further processing of the residual sugars portion of the overall product mixture.
  • the fast-dehydration approach of the WO'136 application is used to generate an aqueous HMF product but with little to none of the residual sugars product portion being generated, and the aqueous HMF product is used for generating the aqueous HMF feed to the oxidation step of an integrated process.
  • aqueous HMF product portion from the dehydration step is merely diluted by addition of dilution water to generate an aqueous HMF feed of a desired concentration that then undergoes an oxidation step.
  • the product mixture from the dehydration step is not used directly (except for dilution) to provide the aqueous HMF feed that is then oxidized, but only so much of a residual sugars product portion is produced in the dehydration step and removed from an overall dehydration products mixture as is necessary to avoid excessive deactivation of the ruthenium-based oxidation catalyst or other like difficulties in the subsequent oxidation step, as would otherwise be experienced with the amounts of humins and other degradation byproducts of hexose sugars dehydration that would be generated by aggressively carrying out the dehydration step to generate no residual sugars portion and produce an aqueous HMF product portion that can be used directly (except for dilution) in the subsequent oxidation step to produce furanic oxidation products inclusive of FDCA.
  • FIG. 1 corresponds to FIG. 1 of the WO'136 application, and provides a schematic representation of a process according to WO'136 in a preferred embodiment.
  • FIG. 2 schematically illustrates a process of the present invention according to a first aspect, for carrying out an oxidation of HMF in an aqueous feed comprised of one or more sugar dehydration products inclusive at least of HMF.
  • FIG. 3 shows an integrated process according to the second aspect of the present invention in a preferred embodiment, wherein a process according to the WO'136 application is used to produce an aqueous feed comprising one or more hexose dehydration products inclusive at least of HMF, and HMF in the aqueous feed is oxidized using a catalyst and process according to the instant application.
  • levulinic acid is (like HMF) a hexose dehydration product which can be oxidized by means of the inventive catalyst to provide succinic acid, which like FDCA has been identified as a promising biobased product alternative to conventional petroleum-derived commodities, for example, maleic anhydride, or as providing a biobased starting material for producing a chemical presently made from petroleum-derived feedstocks (for example, 1,4-butanediol, tetrahydrofuran and gamma butyrolactone).
  • FDCA hexose dehydration product
  • succinic acid which like FDCA has been identified as a promising biobased product alternative to conventional petroleum-derived commodities, for example, maleic anhydride, or as providing a biobased starting material for producing a chemical presently made from petroleum-derived feedstocks (for example, 1,4-butanediol, tetrahydrofuran and gamma butyrolactone).
  • Preferred substrates for oxidation are those which can be derived by dehydration from readily available carbohydrates from agricultural raw materials such as starch, cellulose, sucrose or inulin, especially fructose, glucose or a combination of fructose and glucose, though any such carbohydrate source can be used generally.
  • suitable carbohydrate sources include, but are not limited to, hexose, fructose syrup, crystalline fructose, and process streams from the crystallization of fructose.
  • Suitable mixed carbohydrate sources may comprise any industrially convenient carbohydrate source, such as corn syrup.
  • mixed carbohydrate sources include, but are not limited to, hexoses, fructose syrup, crystalline fructose, high fructose corn syrup, crude fructose, purified fructose, high fructose corn syrup refinery intermediates and by-products, process streams from crystallizing fructose or glucose or xylose, and molasses, such as soy molasses resulting from production of soy protein concentrate, or a mixture thereof.
  • the substrates which are fed to the process in the aqueous feed for oxidation are those which are formed by an acid-catalyzed dehydration reaction from fructose, glucose or a combination of these, with 2-hydroxymethyl-5-furfuraldehyde (HMF) again being the sugars dehydration product that is principally of interest.
  • HMF 2-hydroxymethyl-5-furfuraldehyde
  • FIG. 1 of the WO'136 application An embodiment 10 of a process according to WO'136 which may be used or adapted for use for providing an aqueous feed of HMF is shown schematically in FIG. 1 of the WO'136 application, which figure has been reproduced herein as FIG. 1 as well, though those skilled in the art will again appreciate that an aqueous solution of HMF in a concentration of at least five (5) percent by weight can be provided in a number of ways.
  • HMF may be combined with water by carrying out a dehydration of one or more hexose sugars in water, thus generating the HMF and additional water and in effect providing the desired aqueous HMF solution in the process of performing the dehydration.
  • the HMF may be acquired rather than generated, and combined with a separate source of water in the appropriate proportions to provide an aqueous solution of HMF in a concentration of at least five percent by weight.
  • glucose as may be derived from the hydrolysis of starch with acids or enzymes or from the hydrolysis of cellulosic materials is first enzymatically converted in step 12 through use of an isomerase to a mixture of glucose and fructose, in the form of aqueous hexose sugar solution 14 .
  • Processes for making glucose from starch and for converting a portion of the glucose to fructose are well known, for example, in the making of high fructose corn syrups.
  • fructose derived from cane sugar or sugar beets, rather than from an isomerization of glucose may be combined with glucose in a desired proportion.
  • a combination of isomerization of glucose plus blending in of fructose from other known sources may be employed, to provide a combination of glucose and fructose for forming an aqueous hexose sugar solution for further processing.
  • the aqueous hexose sugar solution 14 can correspond to a current high fructose corn syrup product, for example, HFCS 42 (containing 42 percent fructose and 53 percent glucose), HFCS 90 (made from HFCS 42 by additional purification, 90 percent fructose and 5 percent each of glucose and maltose) or HFCS 55 (containing 55 percent fructose, conventionally made from blending HFCS 42 and HFCS 90), so that existing HFCS production capacity can be utilized to make HMF and derivative products to improve asset utilization and improve returns on capital, as HFCS demand and pricing and HMF and HMF derivative demand and pricing would indicate.
  • HFCS 42 containing 42 percent fructose and 53 percent glucose
  • HFCS 90 made from HFCS 42 by additional purification, 90 percent fructose and 5 percent each of glucose and maltose
  • HFCS 55 containing 55 percent fructose, conventionally made from blending HFCS 42 and HFCS 90
  • aqueous hexose sugar solution 14 then undergoes an acid-catalyzed dehydration in step 16 .
  • some of the hexose sugars may not be converted but will remain in the product mixture 18 and would be of a character suited for direct use (if desired) by fermentation to produce ethanol.
  • the acid-catalyzed dehydration step 16 is conducted with rapid heating of the aqueous hexose sugar solution 14 from an ambient temperature to the desired dehydration reaction temperature, and then with rapid cooling of the HMF/unconverted sugar mixture 18 prior to the separation by a solvent extraction or adsorption/desorption step 20 of the fermentation-ready residual sugars product 24 from the HMF product 22 .
  • the time from the introduction of sugar solution 14 until HMF/unconverted sugar mixture begins to be cooled is preferably also limited.
  • the overall exposure of the HMF that is formed to acidic, elevated temperature conditions may be correspondingly limited, so that it is possible to produce little to no humins or other like waste materials.
  • Separation and recovery of the desired products is thereby simplified and levels of HMF and other hexose dehydration products known to inhibit ethanol production by fermentation may be reduced in the residual sugars product to an extent whereby the residual sugars product can be used directly for ethanol fermentation if desired (though a number of other uses of the residual sugars product are foreseeable, examples of which are subsequently cited).
  • the degree to which the product mixture 18 can directly be used in this manner will depend in part on the effect on the subsequent oxidation catalyst of the amount of humins and other like byproducts that would be generated in the acid-catalyzed dehydration step 16 , under the aggressive conditions that would be employed for maximizing HMF yield in the product mixture 18 , as well as on other factors such as the value of the furanic oxidation products that can be made from the additional HMF compared to the value of the fermentation or other products that could have been made from the foregone residual sugars product 24 , and the expenses associated with the separations step 20 and with further processing of a residual sugars product 24 .
  • Adsorption in step 20 can be by means of any material which preferentially adsorbs HMF from the residual hexose sugars in the mixture 18 .
  • a material which has been found to be very effective at retaining the HMF and the small amounts of levulinic acid formed is DOWEX® OPTIPORE® V-493 macroporous styrene-divinylbenzene resin (CAS 69011-14-9, The Dow Chemical Company, Midland, Mich.), which has been described by its manufacturer as having a 20-50 mesh particle size, a 46 angstrom mean pore size and 1.16 mL/g pore volume, a surface area of 1100 sq. meters/g and a bulk density of 680 g/liter.
  • An ethanol wash was effective for desorbing most of the adsorbed HMF, and subsequent washing of the resin with acetone provided quantitative recovery of the HMF that was adsorbed.
  • An alternative is AMBERLITETM XADTM-4 polystyrene divinylbenzene polymeric adsorbent resin (CAS 37380-42-0, Rohm & Haas Company, Philadelphia, Pa.), a non-functionalized resin having a 1.08 g/mL dry density, a surface area of 725 square meters per gram, an average pore diameter of 50 angstroms, a wet mesh size of 20-60 and a pore volume of 0.98 mL/gram.
  • adsorbents can be activated carbon, zeolites, alumina, clays, non-functionalized resins (LEWATIT® AF-5, LEWATIT® S7968, LEWATIT® VPOC1064 resins, all from Lanxess AG), Amberlite® XAD-4 macroreticular crosslinked polystryrene divinylbenzene polymer resin (CAS 37380-42-0, Rohm & Haas Company, Philadelphia, Pa.), and cation exchange resins, see U.S. Pat. No. 7,317,116 B2 (Sanborn) and the later U.S. Pat. No. 7,897,794 (Geier and Soper).
  • Desorption solvents may include polar organic solvents, for example, alcohols such as ethanol, amyl alcohol, butanol and isopentyl alcohol, the aforementioned acetone, as well as ethyl acetate, methyl tetrahydrofuran and tetrahydrofuran.
  • polar organic solvents for example, alcohols such as ethanol, amyl alcohol, butanol and isopentyl alcohol, the aforementioned acetone, as well as ethyl acetate, methyl tetrahydrofuran and tetrahydrofuran.
  • Acetone is generally preferred, as in addition to acetone's effectiveness as a desorption solvent, acetone is very low-boiling and readily quantitatively removed by distillation or evaporation.
  • Suitable solvents for solvent extraction include methyl ethyl ketone and especially ethyl acetate, due to the latter's great affinity for HMF and levulinic acid, low boiling point (77 deg. C.) and ease of separation from water.
  • ethyl ketone and especially ethyl acetate, due to the latter's great affinity for HMF and levulinic acid, low boiling point (77 deg. C.) and ease of separation from water.
  • virtually complete recovery of the sugars and of the HMF from mixture 18 was accomplished in WO'136 through a series of ethyl acetate extractions.
  • the residual sugars recovered by other means were still suitable for being directly processed to ethanol in the subsequent ethanol fermentation step 26 , those recovered following the quantitative extraction with ethyl acetate were observed to be significantly less inhibitory even under non-optimal conditions.
  • solvents have been suggested or used in the literature related to HMF and HMF derivative synthesis and recovery in biphasic systems, and these may be appropriate for use.
  • examples of other useful solvents are butanol, isoamyl alcohol, methyl ethyl ketone, methyl isobutyl ketone, diethyl ether, cyclopentyl dimethyl ether, methyl tetrahydrofuran, and methyl butyl ether.
  • Ethanol fermentation step 26 where employed can encompass any known process whereby a hexose sugars feed of the type represented by fermentation-ready sugars stream or portion 24 may be converted to one or more products inclusive of ethanol, at least in some part by fermentation means. Both aerobic and anaerobic processes are thus contemplated, using any of the variety of yeasts (e.g., kluyveromyces lactis, kluyveromyces lipolytica, saccharomyces cerevisiae, s. uvarum, s. monacensis, s. pastorianus, s. bayanus, s. ellipsoidues, candida shehata, c. melibiosica, c.
  • yeasts e.g., kluyveromyces lactis, kluyveromyces lipolytica, saccharomyces cerevisiae, s. uvarum, s. monacensis, s. pastor
  • intermedia or any of the variety of bacteria (e.g., clostridium sporogenes, c. indolis, c. sphenoides, c. sordelli, candida bracarensis, candida dubliniensis, zymomonas mobilis, z. pomaceas ) that have ethanol-producing capability from the fermentation-ready sugars stream or portion 24 under aerobic or anaerobic conditions and other appropriate conditions.
  • the particular yeasts (or bacteria) used and other particulars of the fermentations employing these various yeasts (or bacteria) are a matter for routine selection by those skilled in the fermentation art, though the examples below demonstrate the functionality of one common anaerobic yeast strain, saccharomyces cerevisiae .
  • the sugars stream or portion 24 derives from a process for making the acid dehydration product HMF
  • a yeast or bacteria that has been demonstrated for use particularly with sugars derived from a lignocellulosic biomass through acid-hydrolyzing the biomass and/or a cellulosic fraction from biomass may be preferred.
  • the aerobic bacterium corynebacterium glutamicum R was evaluated in Sakai et al., “Effect of Lignocellulose-Derived Inhibitors on Growth of and Ethanol Production by Growth-Arrested Corynebacterium glutamicum R”, Applied and Environmental Biology, vol. 73, no. 7, pp 2349-2353 (April 2007), as an alternative to detoxification measures against organic acids, furans and phenols byproducts from the dilute acid pretreatment of biomass, and found promising.
  • the fermentation-ready sugars stream or portion 24 can, in whole or in part, also be used for other purposes beyond the production of ethanol.
  • sugars in stream or portion 24 can be recycled to the beginning of the acid dehydration step 16 for producing additional HMF.
  • the hexose sugars represented by stream or portion 24 can also be hydrogenated to sugar alcohols for producing other biobased fuels and fuel additives (other than or in addition to ethanol), see, for example, U.S. Pat. No. 7,678,950 to Yao et al.
  • the sugars in stream or portion 24 can be fermented to produce lysine or lactic acid according to known methods, or used for making another dehydration product such as levulinic acid. Still other uses will be evident to those skilled in the art, given the character of the sugars stream or portion 24 provided by the described process.
  • the acid dehydration step 16 is preferably conducted in a manner to limit the exposure of the HMF that is formed to acidic, elevated temperature conditions that lead to the formation of humins and other like degradation-type materials. Rapid heating of the hexose sugar solution 14 is consequently desirable. Further, once the aqueous hexose solution 14 has reached the desired reaction temperature range, the extent to which the aqueous hexose solution remains subject to the acidic, elevated temperature conditions is preferably also limited as taught and exemplified in the WO'136 application.
  • reaction temperature can be in the range of from 185 degrees to 205 degrees Celsius
  • dry solids loading of hexose sugars in the sugar solution 14 can be from 30 to 50 percent and provide an 8 to 15 percent final dry solids concentration
  • a reaction time can be from 5 to 10 minutes.
  • a final dry solids concentration of 20 percent could not be processed with the same overall sugars accountability, and a lower final dry solids concentration was indicated as preferable.
  • a reaction temperature of 185 degrees Celsius and a reaction time of 10 minutes were observed to provide favorable results.
  • Favored conditions for the recovered sugars in stream or portion 24 may differ from those contemplated for freshly-supplied sugars in sugar solution 14 where recycle is contemplated for making additional HMF product or levulinic acid.
  • the heating to the desired reaction temperature is preferably accomplished in not more than 15 minutes, preferably is accomplished in 11 minutes of less, more preferably in not more than 8 minutes and still more preferably is accomplished in not more than five minutes.
  • rapid feeding of a quantity of ambient hexose sugar solution to a hot aqueous acid matrix gave consistent improvements in one or more of HMF selectivity, yield and overall sugar accountability compared to less rapid feeding, even given the same elapsed time between when the quantity of hexose sugar solution was fully introduced and when cooling was initiated.
  • one suitable means for rapidly heating the sugar solution 14 and the acid catalyst would be direct steam injection.
  • a commercially-available, in-line direct steam injection device the Hydro-Thermal HydroheaterTM from Hydro-Thermal Corporation, 400 Pilot Court, Waukesha, Wis., injects sonic velocity steam into a thin layer of a liquid (such as the sugar solution 14 ) flowing from an inlet pipe through a series of gaps. Steam flow is adjusted precisely through a variable area nozzle to an extent whereby outlet fluid temperatures are claimed to be controllable within 0.5 degrees Fahrenheit over a large liquid turndown ratio.
  • Turbulent mixing takes place in a specifically designed combining tube, with an adjustable degree of shear responsive to adjustments of the steam flow and the liquid flow through (or pressure drop across) the series of gaps.
  • Devices of this general character are described in, for example, U.S. Pat. Nos. 5,622,655; 5,842,497; 6,082,712; and 7,152,851.
  • the highest HMF yield and sugar accountability from HFCS 42 syrup included a system of sulfuric acid (0.5% by wt of sugars), an initial dry solids concentration of 20% and rapid heating of the reaction mixture by direct steam injection by means of a Hydro-Thermal HydroheaterTM with a system back pressure of 1.48-1.52 MPa, gauge (215-220 psig), a steam pressure of 1.90 MPa, gauge (275 psig), a time of 5-6 minutes at the reaction temperatures provided by the direct steam injection and with rapid cooling of the product mixture before pressure relief.
  • the reaction control set point was 200 degrees Celsius, and the maximum temperature achieved at the end of the resting tube was 166 degrees Celsius. HMF was obtained with these conditions in up to 20% molar yield with greater than 90% total sugar accountability. There was virtually no visible production of insoluble humins.
  • the highest HMF yield and sugar accountability included a system of sulfuric acid (0.5% by wt of sugars), an initial dry solids concentration of 10%, and rapid heating of the reaction mixture by direct steam injection with a system back pressure of 1.03 MPa, gauge (150 psig), a steam pressure of 1.38 MPa, gauge (200 psig), a time of 11 minutes at the reaction temperatures provided by the direct steam injection and with rapid cooling of the product mixture before pressure relief.
  • the reaction control set point was 185 degrees Celsius, and the maximum temperature achieved at the end of the resting tube was 179 degrees Celsius.
  • HMF was obtained from HFCS 90 with these conditions up to 31% molar yield with greater than 95% total sugar accountability. There was again virtually no visible production of insoluble humins.
  • the WO'136 application prescribes rapid cooling of the mixture 18 as a preferred further measure to limit the exposure of the HMF product to elevated temperatures and acidic conditions, and describes various ways in which this rapid cooling could be accomplished prior to the use of adsorption, solvent extraction, or a combination of these in separation step 20 as previously described, to yield an HMF product stream or portion 22 and a fermentation-ready sugars stream or portion 24 which can optionally be supplied to an ethanol fermentation step 26 for producing an ethanol product 28 .
  • an integrated process as schematically illustrated in FIG.
  • an oxidation process 30 in isolation, in which an aqueous feed 32 comprising one or more dehydration products inclusive at least of HMF in a concentration of at least about five percent by weight (which aqueous feed 32 may be obtained from a process as described in the WO'136 application, or as previously indicated, may be obtained from any of a number of other sources or by other means) is processed in the presence of an HMF oxidation catalyst according to the present invention to yield products inclusive of FDCA.
  • the aqueous feed 32 undergoes oxidation by combination with an oxygen source 34 (which can be air, oxygen-enriched air, oxygen or a combination of oxygen with one or more other, inert gases) in a reactor 36 , in the presence of a heterogeneous ruthenium-based catalyst, under conditions which are effective to carry out the oxidation.
  • an oxygen source 34 which can be air, oxygen-enriched air, oxygen or a combination of oxygen with one or more other, inert gases
  • a reactor 36 in the presence of a heterogeneous ruthenium-based catalyst, under conditions which are effective to carry out the oxidation.
  • a product 38 comprising FDCA is thereby produced.
  • the catalyst employs ruthenium as the sole active catalyst metal.
  • the catalyst is unsupported.
  • the catalyst is an unsupported ruthenium oxide catalyst, and requires neither prior base treatment or a basic support to be fundamentally effective.
  • the unsupported ruthenium oxide catalyst according to our studies does, however, demonstrate some differences in performance based on the pH of the incoming aqueous feed 32 at lower oxidation temperatures; at lower temperatures, a neutral pH favors FDCA production while higher temperatures were observed to be less sensitive to the pH of the incoming aqueous feed 32 .
  • Suitable reaction temperatures in this regard range from about 70 degrees Celsius to about 170 degrees Celsius, preferably are in the range of from about 85 degrees Celsius to about 160 degrees Celsius, and more preferably are in the range of from about 90 degrees Celsius to about 150 degrees Celsius.
  • the selectivity to certain oxidation products is to a degree dependent on the pH of the incoming aqueous feed; at basic values, selectivity to FDCA is reduced and production of maleic, succinic and fumaric acids increases.
  • differences in the pH of the incoming aqueous feed had comparatively little effect on product distribution.
  • the catalyst loading can be from 0.5 to 30 percent by weight based on the weight of HMF in the aqueous feed, but preferably is used in the range of from 1 to 20 percent by weight based on the weight of HMF in the aqueous feed, and more preferably is employed at from 3 to 15 percent by weight based on the weight of HMF in the aqueous feed.
  • the HMF concentration in the aqueous feed is at least 5 percent by weight up to 30 percent by weight, preferably is from 5 percent by weight of the aqueous feed to 20 percent by weight of the feed, and more preferably is from 5 percent to 15 percent by weight of the aqueous feed.
  • the source of oxygen for performing the oxidation can be oxygen, oxygen-enriched air, air or another mixture of oxygen with one or more inert gases, for example, carbon dioxide.
  • the oxygen source is simply oxygen. From 0.5 MPa to 10 MPa (5 to 100 bar) of oxygen is present, though preferably oxygen is present at from 2.0 MPa to 9.0 MPa (20 to 90 bar) and more preferably is present at from 3.0 to 7.0 MPa (30 to 70 bar).
  • Batch reaction times or average residence times in a continuous reactor will be from 1 to 26 hours, preferably will be from 2 to 20 hours, and more preferably will be from 3 hours to 15 hours.
  • Reactor 36 can be configured in several ways to carry out the oxidation step. Because FDCA is sparingly soluble in water at ambient temperatures and because a heterogeneous solid ruthenium-based catalyst is employed, separation of the FDCA as it is formed from the solid heterogeneous catalyst is an important design consideration. In one embodiment, FDCA is hot-filtered away from the catalyst, by maintaining the temperature of the products above a temperature at which the FDCA remains water-soluble. This manner of operation would lend itself to a continuous fixed-bed, multitubular reactor design.
  • the FDCA could be separated from the heterogeneous catalyst in a multi-vessel slurry process, by pumping a slurry of FDCA solids and of the ruthenium-based heterogeneous catalyst (e.g., unsupported ruthenium oxide) in water into a second vessel following the reactor 36 wherein the FDCA is dissolved in a solvent which substantially does not solubilize the catalyst, for example, methanol, then the FDCA/methanol solution is withdrawn from the vessel and the solid catalyst returned to the reactor 36 . Evaporation of the methanol would then provide a high purity FDCA solid product.
  • a solvent which substantially does not solubilize the catalyst for example, methanol
  • a semi-batch stirred tank configuration can be considered wherein the catalyst is contained in baskets, as in a Carberry or Robinson-Mahoney type reactor, and the stirred tank taken offline for washing with methanol to remove FDCA solids deposited in the reactor and on the catalyst.
  • Still another approach for dealing with the limited solubility of FDCA in water would involve forming an FDCA derivative in the reactor 36 that is substantially more soluble than FDCA, so that the FDCA derivative can be removed in solution from the reactor 36 .
  • the FDCA derivative for example, the dimethyl ester of FDCA, may have beneficial applications of its own, or FDCA could be regenerated from the FDCA derivative by further processing according to known methods.
  • aqueous feed 32 and the oxidation of HMF contained in aqueous feed 32 can take place independently of one another in time and/or place, in a preferred embodiment 40 illustrated schematically in FIG. 3 , preferably the dehydration of hexose sugars in an aqueous solution to provide an aqueous feed containing HMF and the subsequent oxidation of the HMF in such feed are accomplished together in an integrated process.
  • the preferred embodiment 40 has been summarized previously in relation to different modes of practicing a fast dehydration process of the type described in the WO'136 application, according to a second aspect of the present invention, but in general involves carrying out an acid-catalyzed dehydration of an aqueous hexose sugars solution 42 in a dehydration reactor 44 .
  • the dehydration of the hexose sugars in the solution 42 produces an aqueous HMF product 46 and optionally a residual sugars product 48 that may be obtained as a separate product from the aqueous HMF product 46 , by carrying out a solvent extraction or adsorption/desorption step as described in relation to FIG. 1 (as step 20 ) to separate the residual sugars after the dehydration step from the HMF generated in the dehydration step.
  • the principal desired overall product(s) are the furanic oxidation products such as FDCA that are obtained by oxidizing HMF from the dehydration step
  • the residual sugars product 48 will not be produced as a co-product, or if produced will be produced only for recycle back for joinder with the hexose sugars in solution 42 , and with only so much of the residual sugars being produced in product 48 as necessary to avoid excessive deactivation of the ruthenium-based oxidation catalyst or other like difficulties in the subsequent oxidation step yet to be described.
  • Aqueous HMF product 46 is then conventionally diluted with the addition of water 50 to yield an aqueous HMF feed 51 to the oxidation step.
  • the aqueous HMF feed 51 is combined with a source of oxygen 52 in a suitable oxidation reactor 54 in the presence of a ruthenium-based heterogeneous catalyst (not shown) and under suitable conditions for carrying out the oxidation, and furanic oxidation products including FDCA are produced in product 56 .
  • the oxidation reactor 54 and associated process can be as described in FIG. 2 above.
  • a series of HMF oxidation reactions was performed at different temperatures with two sets of otherwise constant reaction conditions on a bench scale, using a Parr multireactor system (Parr Instrument Company, Moline, Ill.). For each run under a given set of conditions, a 75 mL reaction chamber was charged with a solution of HMF in water and ruthenium oxide and pressured with an oxygen source. The solution was heated to a desired temperature over a period of 20-30 minutes, accompanied by magnetic stirring at a controlled rate of 850 rpm. The reaction was continued for a time, then the solution was cooled and the heterogeneous mixture filtered to remove the solids. The oxidized products in the solids were isolated by washing the solids with methanol and then removing the methanol by rotary evaporation. HPLC analysis was performed on the filtrate and the solids after methanol washing. The catalyst was recovered and recycled.
  • HMF was oxidized at different reactor temperatures over a 3 hour reaction time with 10% dry solids, 10% ruthenium oxide catalyst by weight of HMF at 6.0 MPa (60 bar) of oxygen.
  • an additional four runs were conducted at various temperatures with 5% dry solids, 10% ruthenium oxide catalyst at 7.0 MPa (70 bar) of oxygen for a 6 hour reaction time. The results are shown for comparison in Table 1B, and demonstrate that the amount of HMF converted, product yields and overall accountability can be influenced by the reaction temperature employed.
  • aqueous HMF solution comprised of HMF (5% on a dry solids basis) was pressurized to 3.0 MPa (30 bar) with oxygen and heated to 100 degrees Celsius slowly over a period of 25 minutes.
  • no metal oxide was added to the aqueous HMF solution, while in the second instance, the same ruthenium oxide oxidation catalyst as used in previous examples was then added in the same proportion (at 10% by weight of HMF), and in the third instance, the ruthenium oxide was joined by zirconium acetate at 1% by weight of the HMF.
  • the product mixtures from the three runs were rapidly cooled as in previous examples and analyzed by HPLC.
  • FDCA 2,5-furandicarboxylic acid (or dehydromucic acid)
  • FFCA formylfurancarboxylic acid
  • HMFCA hydroxymethylfurancarboxylic acid
  • DFF diformylfuran

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